12.

1 Primary Aluminum Production

12.1.1 General1

Primary aluminum refers to aluminum produced directly from mined ore. The ore is refined and
electrolytically reduced to elemental aluminum. There are 13 companies operating 23 primary aluminum
reduction facilities in the U. S. In 1991, these facilities produced 4.5 million tons of primary aluminum.

12.1.2 Process Description2-3

Primary aluminum production begins with the mining of bauxite ore, a hydrated oxide of aluminum
consisting of 30 to 56 percent alumina (Al2O3) and lesser amounts of iron, silicon, and titanium. The ore is
refined into alumina by the Bayer process. The alumina is then shipped to a primary aluminum plant for
electrolytic reduction to aluminum. The refining and reducing processes are seldom accomplished at the same
facility. A schematic diagram of primary aluminum production is shown in Figure 12.1-1.

12.1.2.1 Bayer Process Description -

In the Bayer process, crude bauxite ore is dried, ground in ball mills, and mixed with a preheated
spent leaching solution of sodium hydroxide (NaOH). Lime (CaO) is added to control phosphorus content
and to improve the solubility of alumina. The resulting slurry is combined with sodium hydroxide and
pumped into a pressurized digester operated at 221 to 554EF. After approximately 5 hours, the slurry of
sodium aluminate (NaAl2OH) solution and insoluble red mud is cooled to 212EF and sent through either a
gravity separator or a wet cyclone to remove coarse sand particles. A flocculent, such as starch, is added to
increase the settling rate of the red mud. The overflow from the settling tank contains the alumina in solution,
which is further clarified by filtration and then cooled. As the solution cools, it becomes supersaturated with
sodium aluminate. Fine crystals of alumina trihydrate (Al2O3 • 3H2O) are seeded in the solution, causing the
alumina to precipitate out as alumina trihydrate. After being washed and filtered, the alumina trihydrate is
calcined to produce a crystalline form of alumina, which is advantageous for electrolysis.

12.1.2.2 Hall-Heroult Process -

Crystalline Al2O3 is used in the Hall-Heroult process to produce aluminum metal. Electrolytic
reduction of alumina occurs in shallow rectangular cells, or "pots", which are steel shells lined with carbon.
Carbon electrodes extending into the pot serve as the anodes, and the carbon lining serves as the cathode.
Molten cryolite (Na3AlF6) functions as both the electrolyte and the solvent for the alumina. The electrolytic
reduction of Al2O3 by the carbon from the electrode occurs as follows:

2Al2O3 % 3C 6 4Al % 3CO2 (1)

Aluminum is deposited at the cathode, where it remains as molten metal below the surface of the
cryolite bath. The carbon anodes are continuously depleted by the reaction. The aluminum product is tapped
every 24 to 48 hours beneath the cryolite cover, using a vacuum siphon. The aluminum is then transferred to
a reverberatory holding furnace where it is alloyed, fluxed, and

2/98 Metallurgical Industry 12.1-1

 Figure 12.1-1. Schematic diagram of aluminum production process. (Source Classification
Codes in parentheses.)
12.1-2 EMISSION FACTORS 2/98
degassed to remove trace impurities. (Aluminum reverberatory furnace operations are discussed in detail in
Section 12.8, "Secondary Aluminum Operations".) From the holding furnace, the aluminum is cast or
transported to fabricating plants.

Three types of aluminum reduction cells are now in use: prebaked anode cell (PB), horizontal stud
Soderberg anode cell (HSS), and vertical stud Soderberg anode cell (VSS). Most of the aluminum produced
in the U. S. is processed using the prebaked cells.

All three aluminum cell configurations require a "paste" (petroleum coke mixed with a pitch binder).
Paste preparation includes crushing, grinding, and screening of coke and blending with a pitch binder in a
steam jacketed mixer. For Soderberg anodes, the thick paste mixture is added directly to the anode casings.
In contrast, the prebaked ("green") anodes are produced as an ancillary operation at a reduction plant.

In prebake anode preparation, the paste mixture is molded into green anode blocks ("butts") that are
baked in either a direct-fired ring furnace or a Reid Hammer furnace, which is indirectly heated. After
baking, steel rods are inserted and sealed with molten iron. These rods become the electrical connections to
the prebaked carbon anode. Prebaked cells are preferred over Soderberg cells because they are electrically
more efficient and emit fewer organic compounds.

12.1.3 Emissions And Controls2-10

Controlled and uncontrolled emission factors for total particulate matter, gaseous fluoride, and
particulate fluoride are given in Table 12.1-1. Table 12.1-2 gives available data for size-specific particulate
matter emissions for primary aluminum industry processes.

In bauxite grinding, hydrated aluminum oxide calcining, and materials handling operations, various
dry dust collection devices (centrifugal collectors, multiple cyclones, or Electrostatic precipitators (ESPs)
and/or wet scrubbers) have been used. Large amounts of particulate are generated during the calcining of
hydrated aluminum oxide, but the economic value of this dust leads to the use of extensive controls which
reduce emissions to relatively small quantities.

Emissions from aluminum reduction processes are primarily gaseous hydrogen fluoride and
particulate fluorides, alumina, carbon monoxide, carbon dioxide (CO2), volatile organics, and sulfur dioxide
(SO2) from the reduction cells. The source of fluoride emissions from reduction cells is the fluoride
electrolyte, which contains cryolite, aluminum fluoride (AlF3), and fluorospar (CaF2). The dissociation of the
molten cryolite is the source of the perfluorinated carbons (PFCs) —
tetrafluoromethane (CF4) and hexafluoroethane (C2F6) — which are formed during anode effects. The
factors related to the formation of PFCs are not currently well understood, but they can be formed either by
direct reaction of the fluorine with the carbon anode or electrochemically.11 The emission factors for CF4 and
C2F6 presented here should be used with caution due to the lack of information on their formation.
Table 12.1-3 presents emission factors for greenhouse gases. The CO2 emission factors shown in
Table 12.1-3 assume that all of the carbon used in the production process is emitted as CO2. While some of
the carbon is emitted as CO, there is insufficient data to develop emission factors for CO. Therefore, the
carbon emitted as CO is treated here as CO2 because it is assumed that it will eventually be oxidized to CO2
after being emitted. Because the primary source of carbon in the anodes is petroleum coke (some is also from
the pitch binder), care must be taken not to double count CO2 emissions in a greenhouse gas emissions
inventory if the CO2 emissions from aluminum production are also accounted for as a non-fuel use of
petroleum coke.

2/98 Metallurgical Industry 12.1-3

 Particulate emissions from reduction cells include alumina and carbon from anode dusting, and
cryolite, aluminum fluoride, calcium fluoride, chiolite (Na5Al3F14), and ferric oxide. Representative size
distributions for fugitive emissions from PB and HSS plants, and for particulate emissions from HSS cells,
are presented in Table 12.1-2.

Emissions from reduction cells also include hydrocarbons or organics, carbon monoxide, and sulfur
oxides. These emission factors are not presented here because of a lack of data. Small amounts of
hydrocarbons are released by PB pots, and larger amounts are emitted from HSS and VSS pots. In vertical
cells, these organics are incinerated in integral gas burners. Sulfur oxides originate from sulfur in the anode
coke and pitch, and concentrations of sulfur oxides in VSS cell emissions range from 200 to 300 parts per
million. Emissions from PB plants usually have SO2 concentrations ranging from 20 to 30 parts per million.

Emissions from anode bake ovens include the products of fuel combustion; high boiling organics
from the cracking, distillation, and oxidation of paste binder pitch; sulfur dioxide from the sulfur in carbon
paste, primarily from the petroleum coke; fluorides from recycled anode butts; and other particulate matter.
Emission factors for these components are not included in this document due to insufficient data.
Concentrations of uncontrolled SO2 emissions from anode baking furnaces range from 5 to 47 parts per
million (based on 3 percent sulfur in coke).

High molecular weight organics and other emissions from the anode paste are released from HSS and
VSS cells. These emissions can be ducted to gas burners to be oxidized, or they can be collected and recycled
or sold. If the heavy tars are not properly collected, they can cause plugging of exhaust ducts, fans, and
emission control equipment.

A variety of control devices has been used to abate emissions from reduction cells and anode baking
furnaces. To control gaseous and particulate fluorides and particulate emissions, 1 or more types of wet
scrubbers (spray tower and chambers, quench towers, floating beds, packed beds, venturis) have been applied
to all 3 types of reduction cells and to anode baking furnaces. In addition, particulate control methods such as
wet and dry electrostatic precipitators (ESPs), multiple cyclones, and dry alumina scrubbers (fluid bed,
injected, and coated filter types) are used on all 3 cell types and with anode baking furnaces.

The fluoride adsorption system is becoming more prevalent and is used on all 3 cell types. This
system uses a fluidized bed of alumina, which has a high affinity for fluoride, to capture gaseous and
particulate fluorides. The pot offgases are passed through the crystalline form of alumina, which was
generated using the Bayer process. A fabric filter is operated downstream from the fluidized bed to capture
the alumina dust entrained in the exhaust gases passing through the fluidized bed. Both the alumina used in
the fluidized bed and that captured by the fabric filter are used as feedstock for the reduction cells, thus
effectively recycling the fluorides. This system has an overall control efficiency of 99 percent for both
gaseous and particulate fluorides. Wet ESPs approach adsorption in particulate removal efficiency, but they
must be coupled to a wet scrubber or coated baghouse to catch hydrogen fluoride.

Scrubber systems also remove a portion of the SO2 emissions. These emissions could be reduced by
wet scrubbing or by reducing the quantity of sulfur in the anode coke and pitch (i.e., calcining the coke).

The molten aluminum may be batch treated in furnaces to remove oxide, gaseous impurities, and
active metals such as sodium and magnesium. One process consists of adding a flux of chloride and fluoride
salts and then bubbling chlorine gas, usually mixed with an inert gas, through the molten mixture. Chlorine

12.1-4 EMISSION FACTORS 2/98

 The molten aluminum may be batch treated in furnaces to remove oxide, gaseous impurities,
and active metals such as sodium and magnesium. One process consists of adding a flux of chloride
and fluoride salts and then bubbling chlorine gas, usually mixed with an inert gas, through the molten
mixture. Chlorine reacts with the impurities to form HCl, Al2O3, and metal chloride emissions. A dross
forms on the molten aluminum and is removed before casting.

Potential sources of fugitive particulate emissions in the primary aluminum industry are bauxite
grinding, materials handling, anode baking, and the 3 types of reduction cells (see
Table 12.1-1). These fugitive emissions probably have particulate size distributions similar to those
presented in Table 12.1-2.

12.1.4 Changes to Section Since 10/86

• Reformatted in 1995 for the 5th Edition.

• For Supplement D to the 5th Edition, the tables with metric units were removed and
some text and emission factors were added for the Greenhouse gases (CO2, CF4, and
C2F6).

April 2007

• Editorial corrections were made. In Table 12.1-2, the total cumulative emissions factor
for Prebake Aluminum Cells was corrected from 2.5 to 5.0 lb/ton.
• Notes D and E were added to the table to clarify emissions factors and size
distributions.
• Source classification codes were added to Table 12.1-3.

2/98 Metallurgical Industry 12.1-5

 Table 12.1-1. EMISSION FACTORS FOR PRIMARY ALUMINUM
PRODUCTION PROCESSES (lb/ton Al produced)a
EMISSION FACTOR RATING: A

Total Gaseous Particulate

Operation Particulateb Fluoride Fluoride Reference

Bauxite grindingc
(SCC 3-03-000-01)
Uncontrolled 6.0 Neg Neg 1,3
Spray tower 1.8 Neg Neg 1,3
Floating bed scrubber 1.7 Neg Neg 1,3
Quench tower and spray
screen 1.0 Neg Neg 1,3
Aluminum hydroxide calciningd
(SCC 3-03-002-01)
Uncontrollede 200.0 Neg Neg 1,3
Spray tower 60.0 Neg Neg 1,3
Floating bed scrubber 56.0 Neg Neg 1,3
Quench tower 34.0 Neg Neg 1,3
ESP 4.0 Neg Neg 1,3
Anode baking furnace
(SCC 3-03-001-05)
Uncontrolled 3.0 0.9 0.1 2,12-13
Fugitive (SCC 3-03-001-11) ND ND ND NA
Spray tower 0.75 0.04 0.03 12
ESP 0.75 0.04 0.03 2
Dry alumina scrubber 0.06 0.009 0.002 2,12
Prebake cell
(SCC 3-03-001-01)
Uncontrolled 94.0 24.0 20.0 1-2,12-13
Fugitive (SCC 3-03-001-08) 5.0 1.2 1.0 2,12
Emissions to collector 89.0 22.8 19.0 2
Multiple cyclones 19.6 22.8 4.2 2
Dry alumina scrubber 1.8 0.2 0.4 2,12
Dry ESP plus spray tower 4.5 1.4 3.4 2,12
Spray tower 112.8 1.4 3.8 2
Floating bed scrubber 112.8 0.5 3.8 2
Coated bag filter dry scrubber 1.8 3.4 0.4 2
Crossflow packed bed 26.3 6.7 5.6 12
Dry plus secondary scrubber 0.7 0.4 0.3 12

12.1-6 EMISSION FACTORS 2/98

 Table 12.1-1 (Cont.)

Total Gaseous Particulate

Operation Particulateb Fluoride Fluoride Reference

Vertical Soderberg stud cell

(SCC 3-03-001-03)
Uncontrolled 78.0 33.0 11.0 2,12
Fugitive (SCC 3-03-001-10) 12.0 4.9 1.7 12
Emissions to collector 66.0 28.1 9.3 12
Spray tower 16.5 0.3 2.3 2
Venturi scrubber 2.6 0.3 0.4 2
Multiple cyclones 33.0 28.1 4.7 2
Dry alumina scrubber 1.3 0.3 0.2 2
Scrubber plus ESP plus spray
screen and scrubber 7.7 1.5 1.3 2
Horizontal Soderberg stud cell
(SCC 3-03-001-02)
Uncontrolled 98.0 22.0 12.0 2,12
Fugitive (SCC 3-03-001-09) 10.0 2.2 1.2 2,12
Emissions to collector 88.0 19.8 10.8 2,12
Spray tower 22.0 7.5 2.7 2,12
Floating bed scrubber 19.4 0.4 2.4 2
Scrubber plus wet ESP 1.8 0.2 0.2 2,12
Wet ESP 1.8 1.0 0.2 12
Dry alumina scrubber 1.8 0.4 0.2 12
a To convert from lb/ton to kg/Mg, multiply by 0.5. SCC = Source Classification Code. Neg = negligible.
ND = no data. NA = not applicable. Sulfur oxides may be estimated, with an EMISSION FACTOR
RATING of C, by the following calculations.
Anode baking furnace, uncontrolled SO2 emissions (excluding furnace fuel
combustion emissions):
40(C)(S)(1-0.01 K) lb/ton
Prebake (reduction) cell, uncontrolled SO2 emissions:
0.4(C)(S)(K) lb/ton
where:
C = Anode consumption* during electrolysis, lb anode consumed/lb Al
produced
S = % sulfur in anode before baking
K = % of total SO2 emitted by prebake (reduction) cells.

*Anode consumption weight is weight of anode paste (coke + pitch)

before baking.

b Includes particulate fluorides, but does not include condensible organic particulate.
c For bauxite grinding, units are lb of pollutant/ton of bauxite processed.
d For aluminum hydroxide calcining, units are lb of pollutant/ton of alumina produced.
e After multicyclones.

2/98 Metallurgical Industry 12.1-7

12.1-8

Table 12.1-2. UNCONTROLLED EMISSION FACTORS AND PARTICLE SIZE

DISTRIBUTION IN ALUMINUM PRODUCTIONa

EMISSION FACTOR RATING: D (except as noted)

Prebake Aluminum Cellscd HSS Aluminum Cellsd HSS Reduction Cellse

Cumulative Cumulative Cumulative

Cumulative Mass Emission Factor Cumulative Mass Emission Factor Cumulative Mass % Emission Factor
Particle Sizeb (:m) % # Stated Size (lb/ton Al produced) % # Stated Size (lb/ton Al produced) # Stated Size (lb/ton Al produced)
0.625 13 0.67 8 0.8 26 25.5
1.25 18 0.92 13 1.3 32 31.4
EMISSION FACTORS

2.5 28 1.40 17 1.7 40 39.2

5 43 2.15 23 2.3 50 49.0
10 58 2.90 31 3.1 58 56.8
15 65 3.23 39 3.9 63 61.7
Total 100 5.0f 100 10.0 100 98
a
Reference 5. To convert from lb/ton to kg/Mg, multiply by 0.5.
b
Expressed as equivalent aerodynamic particle diameter.
c
EMISSION FACTOR RATING: C
d
Emissions factors and size distributions are fugitive emissions measured from the roof monitor.
e
Emissions factors and size distributions are for primary emissions.
f
Emission factor was corrected 4/07. Editorial correction.
2/98
2/98

Table 12.1-3. GREENHOUSE GAS EMISSION FACTORS FOR PRIMARY ALUMINUM PRODUCTION PROCESSESa

Emission Factor EMISSION

Source Category Pollutant (lb/ton Al produced) FACTOR RATING Notes
Aluminum Production — CO2 3670 C Assumes carbon consumption
Soderberg Processb of 0.50 lb C/lb Al produced.
(SCC 3-03-001-02 and
3-03-001-03)c
Aluminum Production — CO2 3080 C Assumes carbon consumption
Prebake Processb of 0.42 lb C/lb Al produced.
(SCC 3-03-001-01)
Metallurgical Industry

Aluminum Production CF4 1.2 E Industry average. Varies with

(SCC 3-03-001-01, duration of anode effect,
3-03-001-02, frequency, and current
3-03-001-03)c efficiency.
Aluminum Production C2F6 0.12 E Industry average. Varies with
(SCC 3-03-001-01, duration of anode effect,
3-03-001-02, frequency, and current
3-03-001-03)c efficiency.
a
References 11,14-17. To convert from lb/ton to kg/Mg, multiply by 0.5.
b
Double counting of emissions will occur if CO2 emissions from aluminum production are also accounted for as a non-fuel use of petroleum coke in a
greenhouse gas inventory.
c
Source Classification Codes were added to the table 4/07.
12.1-9
References For Section 12.1

1. Mineral Commodity Summaries 1992, U. S. Bureau Of Mines, Department Of The Interior,

Washington, DC.

2. Engineering And Cost Effectiveness Study Of Fluoride Emissions Control, Volume I, APTD-0945,
U. S. Environmental Protection Agency, Research Triangle Park, NC,
January 1972.

3. Air Pollution Control In The Primary Aluminum Industry, Volume I, EPA-450/3-73-004a,

U. S. Environmental Protection Agency, Research Triangle Park, NC, July 1973.

4. Particulate Pollutant System Study, Volume I, APTD-0743, U. S. Environmental Protection

Agency, Research Triangle Park, NC, May 1971.

5. Inhalable Particulate Source Category Report For The Nonferrous Industry, Contract No. 68-02-
3159, Acurex Corporation, Mountain View, CA, October 1985.

6. Emissions From Wet Scrubbing System, Y-7730-E, York Research Corporation, Stamford, CT,
May 1972.

7. Emissions From Primary Aluminum Smelting Plant, Y-7730-B, York Research Corporation,
Stamford, CT, June 1972.

8. Emissions From The Wet Scrubber System, Y-7730-F, York Research Corporation, Stamford, CT,
June 1972.

9. T. R. Hanna and M. J. Pilat, "Size Distribution Of Particulates Emitted From A Horizontal Spike
Soderberg Aluminum Reduction Cell", Journal Of The Air Pollution Control Association, 22:533-
5367, July 1972.

10. Written communication from T. F. Albee, Reynolds Aluminum, Richmond, VA, to A. A. McQueen,
U. S. Environmental Protection Agency, Research Triangle Park, NC, October 20, 1982.

11. Inventory Of U. S. Greenhouse Gas Emissions And Sinks: 1990-1993, EPA 230-R-94-014,
U. S. Environmental Protect in Agency, Office of Policy, Planning and Evaluation, Washington, DC,
p. 27, 1994.

12. Background Information For Standards Of Performance: Primary Aluminum Industry: Volume I,
Proposed Standards, EPA-450/2-74-020a, U. S. Environmental Protection Agency, Research
Triangle Park, NC, October 1974.

13. Primary Aluminum: Guidelines For Control Of Fluoride Emissions From Existing Primary
Aluminum Plants, EPA-450/2-78-049b, U. S. Environmental Protection Agency, Research Triangle
Park, NC, December 1979.

14. Inventory Methods Manual For Estimating Canadian Emissions Of Greenhouse Gases, prepared
by Ortech Corporation, for Environment Canada, Ottawa, Ontario, pp. A.29.4-5, 1994.

12.1-10 EMISSION FACTORS 2/98

15. Greenhouse Gas Emissions In Norway—Inventories, And Estimation Methods, Norwegian State
Pollution Control Authority, Rapport 94.02, p. 22, 1994.

16. Canada's Greenhouse Gas Emissions: Estimations for 1990, Report EPS 5/AP14, prepared by
A.P. Jaques, Environment Canada, Ottawa, Ontario, p. 56, 1992.

17. Air Pollution Engineering Manual, Chapter 14, Metallurgical Industry, Primary Aluminum
Industry, M. Wei, A. Buonicore, and W. Davies, eds., Van Nostrand Reinhold, New York, NY, 1992.

2/98 Metallurgical Industry 12.1-11